United States Patent (19) 11 Patent Number: 4,792,633 Wojtkowski 45 Date of Patent: Dec

United States Patent (19) 11 Patent Number: 4,792,633 Wojtkowski 45 Date of Patent: Dec. 20, 1988

54 PREPARATION OF ORTHO-(ALKYL- OR 4,547,593 10/1985 Ranken ...... 568/54 ARYLTHIO)PHENOLS 4,599,451 7/1986 Wojtkowski ...... 568/54 (75) Inventor: Paul W. Wojtkowski, Wilmington, OTHER PUBLICATIONS DE P. Ranken et al., Synthesis, Feb. 1984, pp. 117-119, (73) Assignee: E. I. Du Pont de Nemours and Alkylthiolation of Phenols. Company, Wilmington, Del. B. Farah et al., J. Organic Chemistry, vol. 28, pp. (21) Appl. No.: 864,226 2807-2809 (1963), Alkylmercaptophenols by Sulfenyla tion of Phenols. 22 Filed: May 19, 1986 (51) Int. Cl." ...... C07C 148/02 Primary Examiner-Mary E. Ceperley (52) U.S. Cl...... 568/46; 568/47; 57 ABSTRACT 568/48; 568/49; 568/50; 568/52; 568/53; 568/54 Strong acids, e.g., aluminosilicates and sulfonic acids (58) Field of Search ...... 568/46, 47, 48, 49, are employed as catalysts for the (alkyl or aryl)thiola 568/52, 53, 54; 560/50 tion of phenols using dialkyl or diaryl disulfides and/or (alkyl- or arylthio)phenols as thiolating agents, and for 56) References Cited the isomerization of (alkyl- or arylthio)phenols, to pre U.S. PATENT DOCUMENTS pare ortho(alkyl- or arylthio)phenols as the predomi 2,923,743 2/1960 Deffs et al...... 568/54 nant products. 3,134,818 5/1964 Farah et al...... 568/54 4,324,920 4/1982. McKinnie et al...... 568/54 17 Claims, No Drawings 4,792,633 1. 2 drocarbylthio)phenols by themselves, in the presence of PREPARATION OF ORTHO-(ALKYL OR strong acids such as crystalline Zeolitic aluminosilicates, ARYLTHIOPHENOLS mixed metal oxides including especially amorphous silica-aluminas, clays, sulfuric or phosphoric acids, al CROSS REFERENCE TO RELATED 5 kyl- or aryl-sulfonic acids, polymer-supported sulfonic APPLICATIONS acids, zirconium phenoxides, or boron trifluoride and U.S. Ser. No. 740,030 filed on May 31, 1985 and is mixtures of the foregoing. sued on July 8, 1986 as U.S. Pat. No. 4,599,451 by P. W. Wojtkowski discloses using zirconium phenoxides as DETAILED DESCRIPTION OF THE catalysts for thiolation. 10 INVENTION The phenols to be thiolated in this process include BACKGROUND OF THE INVENTION phenol itself, catechol, resorcinol, and polynuclear phe 1. Field of the Invention nols such as naphthols. The aryl portion of the phenol This invention relates to a process for the preparation may be linked to or fused with other cyclic systems, of ortho-(alkyl- or arylthio)phenols by using certain 15 including heterocyclic systems such as those containing amorphous and crystalline aluminosilicates and/or cyclooxygen, nitrogen, or sulfur rings. In addition to other strong acids as catalysts for the reaction of phe nols with dialkyl or diaryl disulfides and/or certain hydroxyl, other substituents which do not interfere with (alkyl- or arylthio)phenols as (alkyl or aryl)thiolating the reaction can be present on the phenol as long as at agents, and for the isomerization of (alkyl- or arylthio)- 20 least one orthoposition remains unsubstituted. Suitable phenols. substituents include C1-C6 alkyl groups, Cl, F, I, Br, 2. Description of Related Art OR1, aryl, or aryl substituted with C1-C6 alkyl groups, Ortho-(alkylthio)phenols are used to prepare agricul Cl, F, I, Br, OR1 and where R1 is C1-C6 alkyl groups or tural chemicals such as herbicides. U.S. Pat. No. phenyl. The preferred phenols are phenol, 4-chloro 4,324,920, issued on Apr. 13, 1982 and the article by P. 25 phenol, and 4-methylphenol. Operable phenols are iden F. Ranken et al. entitled "Alkylthiolation of Phenols', tified by the formula Synthesis, February 1984, pp. 117-9 disclose a process for the preparation of ortho-(alkylthio)phenols along OH with lesser amounts of para-(alkylthio)phenols by con tacting phenols with dialkyl disulfides in the presence of 30 aluminum phenoxide catalysts. U.S. Pat. No. 2,923,743, issued on Feb. 2, 1960, discloses a process for the prepa ration of ortho-(alkylthio)phenols by contacting phe nols with dialkyl disulfides in the presence of at least X Y equimolar quantities of condensation agents, such as 35 aluminum chloride, aluminum bromide, ferric chloride, wherein zince chloride, tin tetrachloride, antimony pentachlo X and Y are independently selected from the group ride, or boron fluoride. Examples 4 and 5 of the U.S. consisting of H, OH, C1-C6 alkyl, OR1, Cl, F, I, Br, Pat. No. 2,923,743 show that lesser amounts of ortho aryl, or aryl substsituted with C1-C6 alkyl, OR1, Cl, (alkylthio)phenols relative to the para isomers are pro F, I or Br, or when X and Y are on adjacent carbon duced when the condensation agent is a bleaching earth atoms, they may be taken together to form or activated bleaching earth such as Tonsil (R). CH=CH-CH=CH; and It is disclosed in U.S. Pat. No. 3,134,818 issued May R1 is C1-C6 alkyl or phenyl; 26, 1964, Belgian Pat. No. 626,874, Canadian Pat. No. provided that X and Y cannot simultaneously be OH, 714,094, and Journal of Organic Chemistry, 28, 2807 45 and when X or Y is OH and the other is hydrogen, (1963) that the preparation of para-(alkylthio)phenols the OH cannot be in the para position. along with lesser amounts of ortho-(alkylthio)phenols Thiolating agents usable in this invention include can be effected by reaction of phenols with dialkyl dialkyl and diaryl disulfides, i.e., having the formula disulfides in the presence of acid catalysts such as phos (RS)2. The dialkyl disulfides which are operable in the phoric acid, polyphosphoric acid, concentrated sulfuric 50 present invention include those where the alkyl group acid, alkanesulfonic acid, arenesulfonic acid, and spe has 1-6 carbon atoms but when the alkyl groups contain cific cationic ion-exchange resins. U.S. Pat. No. 4-6 carbon atoms the carbon bonded to the heteroatom 4,547,593 issued Oct. 15, 1985 discloses the preparation must be substituted by one or two hydrogen atoms. of (hydrocarbylthio)phenols by heating one or more Dimethyl disulfide, diethyl disulfide and di-n-propyl mono- or poly(hydrocarbylthio)phenols in the presence 55 disulfide are preferred. of aluminum phenoxide catalysts to redistribute the Diaryl disulfides which are operable include those starting materials. wherein the aryl group is unsubstituted or substituted with one or more substituents including C1-C6 alkyl, Cl, SUMMARY OF THE INVENTION F, I, Br, OR1, aryl where R1 is C1-C6 alkyl or phenyl. A process for the preparation of relatively high levels 60 The term hydrocarbyl as used herein means the alkyl of ortho-(hydrocarbylthio)phenols, e.g. ortho(alkyl-or groups and aryl groups in the above-described disul arylthio)phenols, by reacting at a temperature in the fides. The term (hydrocarbylthio)phenols used herein range 50-250', preferably 110-220', and for a suffi includes mono-(hydrocarbylthio)phenols which can be cient period of time to maximize the desired ortho iso the ortho, meta, and para isomer, di-(hydrocarbylthio)- mer, phenols, having at least one unsubstituted ortho 65 phenols, and poly-(hydrocarbylthio)phenols. position, with a hydrocarbyl disulfide such as methyl Other alkylthiolating agents which can be used singly disulfide, and/or with a (hydrocarbylthio)phenol, such or in combination with disulfides include (alkylthio)- as para-(methylthio)phenol, or by reacting para-(hy phenols, preferably para-(alkylthio)phenols or di-(alkyl 4,792,633 3. 4 thio)phenols, preferably where the alkyl groups are the structure of catalysis. Pore dimensions are determined same as in the dialkyl disulfide described above. (Aryl by the geometry of the aluminosilicate tetrahedra form thio)phenols, preferably para-(arylthio)phenols or di(a- ing the Zeolite channels or cages, with nominal openings rylthio)phenols, can also be used as arylthiolating of 2.6 A for 6-rings, 4.0 A for 8-rings, 5.5 A for 10-rings agents for the preparation of ortho-(arylthio)phenols, and 7.4. A for 12 rings. Pore dimension is related to and can have aryl the same as in the diaryl disulfide catalytic performance, since this characteristic deter described above. In the case of all disubstituted phenols mines whether reactant molecules can enter and prod as alkylthiolating or arylthiolating agents, the preferred uct molecules can exit the zeolite framework. In prac isomers are the ortho,ortho- and ortho,para-. tice, it has been observed that very slight decreases in The mixed metal oxides operable as catalysts in the 10 present invention possess sufficient acidity to be catalyt ring dimensions can effectively hinder or block move ically active for alkyl- or arylthiolation. A discussion of ment of particular reactants or products within a zeolite mixed metal oxides and their acidity along with exam Structure. ples is given in K. Tanabe, Solid Acids and Bases, Aca Useful references generally relating to zeolite struc demic Press, 1970, Chapter 4. The most preferred mixed 15 ture and characterization include the following: metal oxides in this invention are amorphous aluminosil Meier et al., Atlas of Zeolite Structure Types (Interna icates also referred to as amorphous silica-aluminas or tional Zeolite Assn. 1978); simply silica-aluminas. The amorphous aluminosilicates Mumpton, "Natural Zeolites' in Reviews in Mineral are the simplest form of aluminosilicates. ogy 14:1 (1977); Neither silica nor alumina have a strong acidic char 20 Smith, "Origin and Structure of Zeolites' in Zeolite acter. However, in silica-aluminas, the isomorphous Chemistry and Catalysis, ACS Monograph 171 replacement of some tetravalent silicon ions with triva (American Chemical Society, 1976). lent aluminum ions in the tetrahedral silica structure The preferred zeolite is zeolite Y, a large-pore syn creates acidic sites necessary for catalytic activity in the thetic zeolite with a nominal Si/Al ratio of 2.4 which silica-aluminas. The addition of a small amount of water can be described by the formula will govern whether these are Lewis or Bronsted acid 25 sites, and both may be present. Heating a silica-alumina Na56Al57Si36O384.250 H2O. can increase its acidity, for example by lowering its water content since excess water can compete for ab The structure and synthesis of this synthetic zeolite are sorption sites. More complete descriptions of the struc described in Zeolite Molecular Sieves, by D. W. Breck, ture and acidity of silica-aluminas can be found in the 30 John Wiley, 1974. articles by B. C. Gates et al. entitled "Chemistry of Cata The crystal structure of zeolite Y is characterized by lytic Processes' (McGraw-Hill, 1979, Chapter 1) and L. large 26-hedron cages with 12-ring openings, defining H. Little entitled "Infrared Spectra of Adsorbed Species' pore sizes of approximately 7.4A (0.74 nm) which per (Academic Press, 1966, Chapter 7). A wide range of 35 mits entrance of branched-chain hydrocarbons and aro silica-aluminas can be used in this invention provided matic molecules. they have sufficient acidity to be catalytically active for The cationic species Na present in Yzeolites can be alkyl- or arylthiolation. The alumina content can vary exchanged for protons in a conventional ion exchange from 5 to 90%, but the preferred silica-aluminas contain with H+ or by conversion to an ammoniated form 10-60% and more preferably 25-30% alumina. The (NH4Y) which is subsequently converted to the acid amorphous silica-aluminas can be combined with other form by calcination at elevated temperatures. matrix materials, e.g., clay, which does not hinder the An acid form of zeolite Y can also be prepared by catalytic activity under process conditions. The silica introduction of a trivalent ion such as La3+ or other aluminas can be treated under appropriate conditions including atmosphere, time and temperature to improve rare earth ion. An example of such rare-earth ex or restore their catalytic activity. 45 changed Yzeolites is known as SK-500 produced by the Another group of materials which are operable in the Union Carbide Co. present invention include the crystalline alumino-sili Of particular utility for the process of the present cates (zeolites) which are conveniently represented by invention are Si-rich forms of zeolite Y. Examples of the formula: such zeolites are commercial zeolites such as ELZ-10 50 (Si/Al=2.97) or ELZ-20 (Si/Al=3.12) produced by M2/O.Al2O3. x SiO2. y H2O the Union Carbide Co. Another zeolite employed in the present invention is wherein M is a cation of valence n, x 22, and y is a the high silica zeolite Beta described in U.S. Pat. No. number determined by the porosity and the hydration 3,308,069 and U.S. Pat. No. Re. 28,341. The Si/Al ratio state of the zeolite, generally from 2 to 8. In naturally 55 varies from about 5 to 50. The crystal structure of zeo occurring zeolites, M is principally represented by Na, lite Beta is not known, but sorption measurements Ca, K, Mg and Bain proportions usually reflecting their showing a capacity of 20% cyclohexane indicated it to approximate geochemical abundance. The cations M be a large pore zeolite and Martens et al., Zeolites, 4, 98 are loosely bound to the structure and can frequently be (1984) find, from the conversion of n-decane over H, Pt completely or partially replaced with other cations by 60 Beta, that Beta is a large-pore zeolite with 12-membered conventional ion exchange. rings and moderately sized cages. These Zeolite structures are characterized by corner Another zeolite useful in this invention is mordenite linked tetrahedra with Al or Siatoms at centers of tetra which can be described by the formula hedra and oxygen atoms at corners. Such tetrahedra are combined in a well-defined repeating structure compris 65 Na3Al3SiOO96. 24 H2O ing various combinations of 4-, 6-, 8-,10-, and 12-mem bered rings. The resulting framework consists of regu The crystal structure of mordenite is characterized by lar channels and cages, which impart a useful pore parallel channels running along the c-axis and having a 4,792,633 5 6 cross section of 6.7x7.0 A (0.67-0.70 nm). These paral The nature of the differences between acid forms of lel channels are joined by smaller channels which are zeolites as prepared by the above-described techniques not accessible to large organic molecules such as those has not been precisely pinpointed. It has been sug having aromatic ring structures. gested, however, that products of deep-bed calcination Medium-pore high-silica zeolites known generally as conditions contain nonframework Al species which pentasil zeolites and specifically as ZSM-5 and ZSM-11 have dissociated from the zeolite lattice during the de are also preferred and are described in U.S. Pats. Nos. ammoniation process. Freude et al., Zeolites 3:171 3,702,886, and 3,709,979, the articles by Kokotailo et al., (1983) have shown that, according to temperature and The Properties and Applications of Zeolites, Chem. Soc. the degree of deep-bed calcination of zeolite NH4 Y, Spec. Publ. No. 33, London (1979), and Olson et al., J. 10 nonframework Al species containing octahedrally Catalysis 61, 390 (1980). These groups of zeolites are coordinated Al are progressively condensed. Presum identified by the formula: ably such nonframework species function as catalyti cally active sites or as modifiers of other catalyticallyac NanAl,Sig6-O192. 16 H2O tive sites. Such "deep-bed' calcined zeolites are particu 15 larly advantageous for the present invention and gener where n usually varies from 0 to about 8. The structures ally preferred over "shallow-bed' calcined zeolites, but of both ZSM-5 and ZSM-11 contain intersecting chan both types of catalysts will work in the present inven nels made up of 10-membered rings having cross sec tion. tions, pore sizes, of 5-6 A (0.5-0.6nm). The configura Generally, calcination temperatures must be suffi tion of the channels is not critical to the activity, e.g., 20 the ZSM-5 structure contains zig-zag channels inter ciently high to convert substantially all NH4 sites to secting straight channels. The pore size of ZSM-5 re H sites and other acid sites, yet not high enough to duces the formation of di- and highersubstituted (alkyl render significant amounts of the zeolite amorphous. thio)phenols because they are bulkier than the mono The presence of NH4+ in a given sample can be deter substituted phenols and consequently have more diffi 25 mined by infrared measurements. Excessive calcination cultly forming in the channels. can lead to collapse of zeolite crystalline structure and Other medium-pore zeolites with pores defined by an amorphous state, which is to be distinguished from either 10- or 12-membered rings such as offretite, ferri “X-ray amorphous' zeolitic materials. erite, ZSM-34, ZSM-23, and ZSM-35 are operable as In practicing the process of the invention, the zeolite catalysts. Small pore zeolites, such as erionite, whose 30 catalysts of the invention can be combined with another channels are constructed of 8-rings are not preferred material resistant to the temperature and other condi because the phenolic moieties are too large to enter the tions employed in the process. Such matrix materials channels which are less than about 5 A and usually of include synthetic or natural substances such as clays, the order of 4 A (0.4 nm). silica and metal oxides. Acid forms of zeolites are preferred in this invention. 35 The number and strength of acid sites are major fac Acid forms of zeolites can be prepared by a variety of tors in catalytic activity and are related to the aluminum techniques including ammonium exchange followed by content of zeolites. Minimum Al content corresponds to calcination, direct exchange of alkali ions for protons Si/Al ratio of about 1000. using mineral acids or ion exchangers, and by introduc As a measure of acid strength, Miale et al., J. Catal. tion of polyvalent ions (for a discussion of acid sites in 40 6,278 (1966) have used the cracking of n-hexane to zeolites, see J. Dwyer, "Zeolite Structure, Composition determine alpha values. In this test, zeolites are com and Catalysis' in Chemistry and Industry, Apr. 2, 1984). pared in their ability to convert 12.5% n-hexane passed The acid sites produced are generally believed to be of as saturated vapor (25 C.) in a stream of helium over the Bronsted (proton donating) type or of the Lewis the catalyst at 538 C. with a 9 second superficial (electron pair accepting) type. Bronsted sites are gener 45 contact time at a time of 5 minutes after commencing ally produced by deammoniation at low temperatures, flow. exchange with protons, or hydrolysis of polyvalent The table below compares alpha values obtained cations. Lewis sites are believed to arise from dehy from a wide variety of zeolites. The preferred catalysts droxylation of the H zeolites or from the presence of of this invention H ZSM-5, HY, H mordenite and H polyvalent ions. In the acidic zeolite catalysts of the 50 Beta are all observed to have high alpha values, indicat present invention, Bronsted and/or Lewis sites can be ing that one of the characteristics of the zeolite catalyst present. of this invention is their strong acidity. It has previously been established (Kerr, "Hydrogen Zeolite Y, Ultrastable Zeolite Y, and Aluminum-Defi Alpha Values for Zeolite Catalysts cient Zeolites', in Molecular Series, Advances in Chemis 55 Zeolite Alpha Value try Series 121:210 (American Chemical Society (1973)) ZSM-11 40-200 that NH4 zeolites deammoniated by deepbed calcination ZSM-23 310 techniques exhibit properties distinct from those of zeo-. ZSM-35 420 ZSM-34 150-900 lites deammoniated by shallow-bed calcination tech LaY 700 niques. Deep-bed calcination refers to combinations of 60 HY 1200 bed geometry and calcination conditions, e.g., thick HBeta 1000-20,000 beds and/or slow flow of gas over zeolite, which do not H Mordenite > 100,000 result in rapid removal of gaseous N2O and NH3 from HZSM-5 > 100,000 the heated zeolite. In contrast, shallow-bed calcination refers to bed geometries and conditions, e.g., shallow 65 The use of aluminosilicates, both amorphous and beds and rapid stripping of gases from the bed, which crystalline, provide advantages over catalysts described maximize removal of H2O and NH3 from zeolite. Deep in the prior art in the predominant production of the bed conditions are preferred. ortho-isomer in synthetically useful amounts. Alumino 4,792,633 7 8 silicates are not as corrosive as the commonly used drocarbylthio)phenols are also formed in this process, acids such as sulfuric, and are therefore safer and easier albeit in lesser final amounts than the ortho-isomer. In to handle. Most are commercially available. The alumi the case of phenol itself, these di-(hydrocarbylthio)- nosilicate catalysts are not as moisture sensitive as other phenols are typically the 2,4- and 2,6-isomers. If dialkyl materials such as aluminum phenoxide. Certain of the 5 disulfide is used, provision should be made to allow for aluminosilicates provide reaction rates higher than cer the continuous removal of the alkyl mercaptan by tain prior-art catalysts. The aluminosilicates are essen product corresponding to the dialkyl disulfide used. tially insoluble and can be readily separated from the The use of an essentially inert solvent is optional and reaction mixture by simple, inexpensive filtration, and preferably excess phenol is employed as a solvent reac can be reused directly or regenerated if necessary. They 10 tant. The reaction is normally performed at or below can also be employed in fixed beds. atmospheric pressure under an inert atmosphere. Anhy The formation of lower amounts of unwanted di- and drous conditions are not necessary, although excessive higher-substituted (hydrocarbylthio)phenols, which are amounts of moisture which can interfere with the de common by-products of these reactions, can be effected sired reaction are avoided. The product can be isolated by choice of a zeolite aluminosilicate catalyst of appro 15 by conventional methods including fractional distilla priate pore size. Additional advantages of the process in tion of the total reaction product before or preferably this invention include, that the unwanted (hydrocarbyl after separation of any solids therein. thio)phenol isomers such as para-(hydrocarbylthio)- In another preferred embodiment of this invention, phenol and di-(hydrocarbylthio)phenol by-products, ortho-(hydrocarbylthio)phenols are obtained by react which are normally formed in the reaction, can be recy 20 ing a phenol unsubstituted in at least one ortho position cled to shift the products to the desired ortho-isomer. with a thiolating agent which is a (hydrocarbylthio)- The generation of large amounts of malodorous mer phenol, preferably a para-(hydrocarbylthio)phenol, captain by-products, which are common in the prior art and/or an ortho,ortho- and/or ortho,paradi(hydrocar using disulfides as thiolating agents, can be avoided by bylthio)phenol, in the presence of the above-described the use of (hydrocarbylthio)phenols, especially para 25 aluminosilicates, clays, mixed metal oxides besides alu (hydrocarbylthio)phenols or di-(hydrocarbylthio)- minosilicates, alkyl- or arylsulfonic acids, polymer-sup phenols, as the thiolating agents. ported sulfonic acids, sulfuric, phosphoric, or polyphos Other catalysts, besides the above-described crystal phoric acids, borontrifluoride, or zirconium phenoxides line zeolitic aluminosilicates and mixed metal oxides in which the phenoxide is the same as the phenol to be including especially amorphous silica-alumina usable in 30 thiolated. An example is the reaction of phenol itself this invention, depending upon starting materials, are with a para-(alkylthio)phenol to yield ortho-(alkylthio)- strong acids such as clays, sulfuric acid, phosphoric phenol wherein the reaction is allowed to proceed at acid, polyphosphoric acid, alkyl- or arylsulfonic acids, elevated temperature for the period of time which polymer-supported sulfonic acids, boron trifluoride and yields the maximum amount of the desired ortho-iso zirconium phenoxides. 35 re, Clays can be of a wide variety such as montmorillon In another preferred embodiment of this invention, ites, bentonites, etc. The clays are preferably activated ortho-(hydrocarbylthio)phenols are obtained by react before use by treatment with acid, for example by boil ing a phenol unsubstituted in at least one ortho position ing in a dilute mineral acid such as sulfuric or hydro with a mixture of dihydrocarbyl disulfide and (hy chloric acid and then drying. drocarbylthio)phenols, including para- and/or ortho,or Examples of the various alkyl- and arylsulfonic acids tho-di- and/or ortho,para-di-, in the presence of as cata include trifluoromethanesulfonic acid and p-toluenesul lysts aluminosilicates, mixed metal oxides besides alumi fonic acid. Examples of polymer-supported sulfonic nosilicates, clays, alkyl- or arylsulfonic acids, polymer acids include the crosslinked polystyrene cationic ion supported sulfonic acids, boron trifluoride, or zirco exchange resin sold as Amberlyst (R) 15, and the perfluo 45 nium phenoxides to produce improved yields of ortho rinated ion-exchange resin sold as Nafion (E). (hydrocarbylthio)phenols based on the phenol and di The H+ form of the polymer-supported sulfonic sulfide used. The hydrocarbylthio groups of all thiolat acids is preferred. It has been speculated that when ing agents should be the same. Provision should be sulfuric acid is used it reacts with a phenol to form an made to allow by-product hydrocarbylmercaptan to arylsulfonic acid which serves as the catalyst. 50 escape. An example is the reaction of phenol itself with Boron trifluoride can be used as is, or as a complex dimethyl disulfide in the presence of para-(methylthio)- such as boron trifluoride diethyl etherate. Zirconium phenol and di-(methylthio)phenols to produce more phenoxides preferably are fully substituted with the ortho-(methylthio)phenol than in their absence. phenoxide corresponding to the phenol being reacted In another embodiment of this invention, (hydrocar but can be partially substituted with alkoxy or halide 55 bylthio)phenol, especially para-(hydrocarbylthio)- groups. For example, the preferred form of this catalyst phenol, is isomerized to ortho-(hydrocarbylthio)phenol when phenol is a reactant is zirconium tetraphenoxide. in the presence of aluminosilicates, mixed metal oxides In one preferred embodiment of the process of this other than aluminosilicates, clays, sulfuric or phos invention the phenol, having at least one unsubstituted phoric acids, alkyl- or arylsulfonic acids, polymersup ortho-position, is reacted with a dialkyl or diaryl disul 60 ported sulfonic acids, boron trifluoride, or zirconium fide, as thiolating agent in the presence of a catalyst, phenoxides where the phenoxide corresponds to the preferably an amorphous aluminosilicate having about phenol of the (hydrocarbylthio)phenols. 25% alumina or a crystalline zeolitic aluminosilicate This reaction is performed by contacting the para with pores defined by 10- or 12-membered rings and (hydrocarbylthio)phenol with the catalyst, preferably pore size > - 5 A at temperatures in the range 65 an aluminosilicate, and heating at temperatures in the 110-220 C. for a sufficient period of time to allow range 110-220 C. for a sufficient period of time to formation of the maximum amount of the desired ortho allow formation of the maximum amount of the desired isomer. Normally para-, di-, and higher-substituted-(hy ortho-isomer. The reaction is normally performed at or 4,792,633 10 below atmospheric pressure under an inert atmosphere. Anhydrous conditions are not necessary, although ex TABLE I-continued cessive amounts of moisture which can interfere with % Area the reaction are avoided. The product can be isolated Time (Methylthio)phenols by conventional methods as described earlier. (Hours) Pheno Ortho Para Disubstituted The overall results in all the above reactions pro 9 46 30 5 9 duces mono-ortho-(hydrocarbylthio)phenols in greater 1. 46 31 15 8 amounts than para-(hydrocarbylthio)phenols or di-(hy drocarbylthio)phenols when formation of all these iso mers is possible, i.e., is not prevented by substitution on 10 EXAMPLE 2 the phenol starting material. Approximately 3.0 g of para-(methylthio)phenol In the course of these processes, a small amount of higher-substituted-(hydrocarbylthio)phenols are nor along with 1.0 g of H Y (Example 1) zeolite were mally produced also. if the mon-substituted phenol is charged to the apparatus of Example 1. The liquid con desired, the amount of di- and higher(hydrocarbylthio)- 15 tents of the flask were sampled and analyzed as de phenols produced can be lowered by starting with an scribed in Example 1 with the following results re excess of the phenol to be hydrocarbylthiolated. The ported in Table II. amount of di- or higher-(alkylthio)phenols can also be TABLE II reduced by using a zeolitic catalyst of a pore size e.g., % Area 5-6 Angstrom units, which will restrict formation of the 20 Time Temperature (Methylthio)phenols larger disubstituted products. (Hours) (°C) Phenol Ortho Para Disubstituted The processes of the present invention are normally 2 140 17.0 2.7 75.5 14.2 conducted at temperatures of 50-250 C., usually 5 168 25.0 18.4 28.7 25.6 110-220°C., and preferably at 120°-180° C. The molar 8 170 23.6 26.1. 16.8 31.8 ratio of phenol to thiolating agent is 5:1 to 1:3, prefera 25 12 170 28.6 32.7 15.5 18.9 bly 3:1 to 1:1. The amount of catalyst used may cover a wide range depending upon the activity of the particu lar catalyst used. The aluminosilicates, other mixed EXAMPLE 3 metal oxides, polymersupported sulfonic acids, and The apparatus of Example 1 was charged with 1.9 g clays are generally used at catalytic levels in amounts of 30 phenol, 9.4 g phenyl disulfide and 1.0 g H Y zeolite 100 grams to 1 gram per mole of thiolating agent, or (Example 1) and the contents heated under nitrogen at preferably 75 g/mole to 5 g/mole, or more preferably relfux temperatures of 128-138 C. for 22 hours follow 50 g/mole to 10 g/mole. The alkyl- or arylsulfonic acid ing which the liquid contents were analyzed by gas catalysts, zirconium phenoxide catalysts, and sulfuric or chromatography. The following compounds in corre phosphoric acid catalysts are generally used in molar 35 sponding area were detected: phenol (16%), phenyl ratios of catalyst to thiolating agent of 0.5 to 0.01 or disulfide (27%), ortho-(phenylthio)phenol (19%) and preferably 0.2 to 0.05. Boron trifluoride is used in cata para(phenylthio)phenol (10%). lytic amounts, i.e., less than equimolar, relative to the thiolating agent. Polymer-supported sulfonic acid cata EXAMPLES 4-13 lysts can be recovered from a reaction mixture and 40 With reference to Table III, the apparatus of Exam regenerated by known techniques. Zeolitic catalysts can ple 1 was charged with the indicated amount of phenol, be regenerated e.g., by calcining in air at 550 C. for methyl disulfide and catalyst and the contents heated about 4 hours. under nitrogen at the indicated temperatures and time The following Examples are presented to illustrate following which the liquid contents were analyzed by but not to restrict the present invention. 45 gas chromatography. The results are reported in Table EXAMPLE 1. III. In Examples 4 and 7, amorphous silica-alumina was A 25 ml round bottom, glass flask fitted with a con obtained from the Davison Chemical Division, W. R. denser, nitrogen inlet, thermometer and stirring mecha 50 Grace Co., Grade 980-25, 25% Al2O3. nism was charged with 1.0 g phenol, 1.0 g methyl disul In Example 5, Type Y Zeolite LZ-Y82 (NH4Y) fide and 0.5 g H Y zeolite (LZ-Y82 obtained from which is a large-pore zeolite with 12-ring openings Union Carbide Co. heated 4 hr at 575 C. in flowing defining pore sizes of approximately 7.4 A was obtained nitrogen). The contents of the flask were covered with from the Union Carbide Co. and heated 4 hours at 575 a nitrogen blanket and heated until reflux at which time 55 C. in flowing nitrogen to form H Y zeolite. the temperature of the contents was approximately 110 In Example 6, H ZSM-5 which is a medium-pore C. The temperature gradually increased during the zeolite with 10-ring channels having cross sections of reaction. After reflux was established, samples of the approximately 5-6A was prepared by calcination of 10 liquid contents of the flask were removed periodically g of NH4 ZSM-5 in a covered crucible at 550 C. for 10 with a pipette and analyzed by gas chromatography 60 hours. (GC). The results are reported in Table I. In Example 13, the clay is Mineral Colloid BP Mont TABLE I morillonite from George Kaolin Co. refluxed for 1 hour % Area in 5% hydrochloric acid, filtered, washed with water Time (Methylthio)phenols several times, and dried in a vacuum oven at 110 C. (Hours) Phenol Ortho Para Disubstituted 65 In Example C1, silica was obtained from the Aldrich l 61 9 20 0 Chemical So., sold as silica gel, SiO2 (Merck, 35-70 3 54 15 22 2 mesh) 40 A, surface area 675 m2/g, pore volume 0.68 5 48 22 22 5 cm/g equivalent to Merck 10181. 4,792,633 11 12 In Example C2, gamma-alumina was prepared by W. R. Grace Co.) was heated in stagnant air at 390 C. heating Catapal SB (obtained from Conoco, Inc.) at for one hour prior to use. 700 C. for 15 hours. In Example 15, the catalyst was a rare earth ex In Example C3, H. Erionite which is a small-pore changed Type Y zeolite identified as SK-500 and ob zeolite with 8-ring channels having cross sections of tained from Union Carbide Corp. approximately 4A was prepared by calcination of 50 g In Example 16, Hmordenite was prepared by heating of "Linde' natural erionite (E10, Union Carbide Co.) at NH4 mordenite, LZ-M-8, obtained from Union Carbide 500 C. for 10 hours in flowing nitrogen, three ex Co., at 500 C. in a covered crucible for 16 hours. changes in 10% NH4NO3 solution, and a final calcina In Example 17, Zeolite ZSM-5 was prepared from a tion in flowing nitrogen at 500 C. for 10 hours. 10 mixture of 7.20 g Na aluminate, 9.60 g NaOH, 128.0 g of TABLE III % Area Exam- Reactants - Catalyst - - Reaction Conditions - Methylthio)phenois ple Phenol Disulfide Amount Temperature Time Higher No. (grams) (grams) Type (grams) (C) (hours) Phenol Ortho Para Disubstituted Substituted 4. 2.0 2.0 Silica-Alumina 1.0 130 24 38.4 32.6 11.9 4.4 0.3 5a 2.0 2.0 HY Zeolite O 130 22 37.3 27.3 15.3 13.2 6.8 6a 2.0 20 HZSM-5 1.0 130 21 38.5 32.3 24.6 2.7 .5 7 1.0 1.5 Silica-Alumina 1.0 130 24 62.3 20.7 49 2.0 ND 8 1.0 1.5 Conc. H2SO4 0.2 130 4. St.5 22.2 14.8 5.5 ND 9 2.0 3.0b BF3 Diethyl 0.5 17Oc 22 44.3 15. 1.9 NA NA Etherate 10 2.0 3.0 85%. Phosphoric 0.5 170c 22 47.0 22.2 13.6 NA NA Acid 1. 2.0 3.0 Polyphosphoric 0.5 17Oc 22 49.4 21, 6.9 NA NA Acid 12 1.2 3.0 Zirconium 1.0 75c 4. 53.7 9.8 10. NA NA Tetraphenoxide 3 4.0 6.0 Clay 2.0 75 27 54.4 20.0 9.8 NA NA ca 2.0 2.0 Silica 10 130 23.5 100 O O 0 O Ca 2.0 2.0 Gamma-Alumina 10 130 21 100 O O O O Ca 2.0 2.0 HErionite 10 30 22 100 O O O O Contents heated for 2 hours at about 105-115 C. before indicated conditions Para-(methylthio)phenol was used instead of methyl disulfide Contents heated for 24 hours at 135 C. before indicated conditions NA = Not Analyzed ND = None Detected C = Comparative a 50% solution of tetrapropylammonium bromide, 480.0 EXAMPLES 14-26 g Ludox HS-30 colloidal SiO2 and 528.0 g H2O heated With reference to table IV, the indicated amounts of in a Hastelloy C autoclave at 140 C. for 24 hours. The phenol, methyl (unless otherwise noted) disulfide, and product, after washing, filtering and drying, was identi the catalyst were combined and heated under nitrogen 40 fied by X-ray diffraction as the pentasil ZSM-5. The at reflux while allowing alkyl mercaptain corresponding acid form, H. ZSM-5, was prepared by heating the to the disulfide used to escape and the temperature to ZSM-5 in flowing air to 500 C. for 10 hours, exchang increase. The reaction was terminated at the indicated ing three times in 10% NH4NO3 at 80 C., and heating temperatures and heating times which generally corre the product NH4 ZSM-5 to 540 C. for 10 hours in spond in these and other examples to the point where 45 flowing N2. For Example 18, this catalyst was heated at not further products formed and gas chromagraphic 550 C. for 4 hours in a mixture of flowing steam (200 analysis indicated no further increases in the amount of cc/hr H2O) and N2 (1000 cc/min), i.e., shallow-bed mono-ortho-(alkylthio)phenol product. The reaction conditions, to produce steamed H. ZSM-5. mixture was then permitted to cool to room tempera NH4 ELZ-10 was prepared for Examples 19-24 by ture and then filtered. The remaining solids were thor 50 contacting 50 g of "Linde' Na ELZ-10, a Y zeolite oughly washed with ether. The washings and initial obtained from the Union Carbide Co. having a typical filtrate were combined and volatiles and removed on a Si/A ratio of 2.97, four times with a 10% NH4NO3 rotary flash evaporator following which the nonvola solution at ~80 C. with filtering in between exchanges tiles were analyzed by gas chromatography. The results to produce NH4 ELZ-10. NH4 ELZ-10 was heated are reported in Table IV. 55 slowly in a covered crucible from 25 to 500 C. and In Example 14, amorphous silica-alumina (25% Al- held at 500 C. for 16 hours, i.e., deep-bed conditions, to 2O3, Grade SMR7-S198, Davison Chemical Division, produce H ELZ-10. Amorphous silica-alumina in Examples 25 and 26 is that used in Table III. TABLE IV Reaction Mixture Reactants Catalyst Reaction Conditions (Alkylthio)phenols Example Phenol Disulfide Amount Temperature Time Phenol Ortho- Para- Di No. (grams) (grams) Type (grams) (C.) (hours) (grams) (grams-% yield) (grams) (grams) 14 6.3 4.2 Silica-Alumina 25 84. 9 2.4 2.5-40 1. 1. 15 2.5 8.4 SK-500 2.5 88 10 4.9 3.7-29 2.2 1.3 16 12.5 8.4 H Mordenite 2.5 18 6.5 5.3 4.0-32 2.6 1.0 17 12.5 8.4 HZSM-5 2.5 71 7 S.6 3.7-30 2.5 0.2 4,792,633 13 14 TABLE IV-continued Reaction Mixture Reactants - Catalyst - Reaction Conditions - (Alkylthio)phenols - - Example Phenol Disulfide Amount Temperature Time Phenol Ortho- Para- Di No. (grams) (grams) Type (grams) (°C) (hours) (grams) (grams-% yield) (grams) (grams) Steamed 18 2.5 8.4 HZSM-5 2.5 182 13 5.4 4.5-36 3.0 0.5 19 25 16.8 HELZ-10 5.0 184 7 0.9 10.5-42 NA NA 20 12.5 8.4 HELZ-10 2.5 195 7b. 5.0 5.4-43 2.3 2.3 21 25 8.4 HELZ-10 2.5 181 7 15.9 6.5-52 3.3 0.5 22 12.5 8.4 HELZ-100 2.7 90 8 5.1 5.0-40 2.3 2.0 23 12.5 8.4 HELZ-10d 2.7 140 6 9.3 2.1-17 .0 1.0 24 0.0 6.7 HELZ-10 2.4 171 4. 4.0 3.8-38 2.1 0.9 25 12.5 10.9f Silica-Alumina 2.5 181 16.5 4.3 51-37 NA NA 26 12.5 i3.43 Silica-Alumina 2.5 80 24.5 4.1 5.4-36 NA NA The reaction mixture was vacuum distilled directly without removal of catalyst through a 5'Vigreux column and 22.3 gms of distillate were collected at 95-150 C. at 30 mm Hg and analyzed by gas chromatography which indicated only two major components. Further heating at 175° C. produced no further reaction. Recovered from Example 20 - no additional treatment. Recovered from Example 22 - no additional treatment. EthylRecovered disulfide. from Example 23 - regenerated by heating in air at 500' C. for 16 hours, 8-Propyl disulfide. NA = Not Analyzed. yield), para-(methylthio)phenol (2.7g), and di-(methyl EXAMPLE 27 thio)phenols (2.4 g). Preparation of ortho-(Methylthio)phenol 25 EXAMPLE 28 NH4 ELZ-20 was prepared by contacting 50 g of Preparation of ortho-(Methylthio)phenol "Linde' Na ELZ-20, obtained from the Union Carbide Zeolite Beta was prepared by heating a mixture of Co., four times with a 10% NH4NO3 solution at ~80 11.6 g Na aluminate, 116 mL tetraethylammonium C. with filtering in between exchanges to produce NH4 30 (TEA) hydroxide and 290.7 g of Ludox LS colloidal ELZ-20. NH4 ELZ-20 was heated slowly in a covered SiO2 in an autoclave at 150 C. for 6 days according to crucible from 25 to 500 C. and held at 500 C. for 16 U.S. Pat. No. 3,308,069 issued on May 7, 1967. The hours, i.e., deep-bed conditions, to produce HELZ-20. product after washing, filtering and drying at 110' C. Phenol (12.5g, 0.13 moles), methyl disulfide (8.4g, was identified by X-ray diffraction as TEA Beta. The 0.089 moles), and HELZ-20 (2.5 g) were combined and 35 acidic form, H. Beta, was prepared by exchanging three heated under nitrogen at reflux for 3 hours during times in 10% NH4NO3 solution and heating the filtered which the temperature increased to 180° C. and GC and dried product at 1 C./min to 540 C. for 10 hours. analysis indicated no further increase in the amount of Phenol (12.5g, 0.13 moles), methyl disulfide (8.4g, ortho-(methylthio)phenol. Methyl mercaptan was al 0.089 moles), and H Beta (2.5 g) were combined and lowed to escape continuously. The mixture was cooled 40 heated under nitrogen at reflux while methyl mercaptan to room temperature and filtered. The catalyst was was allowed to escape continuously. Periodic analysis washed several times with ether and allowed to dry by GC is shown in Table V. leaving solid weighing 3.2 g. The filtrate and ether washings were combined, and volatiles were removed TABLE V on a rotary flash evaporator leaving 15.2 g of liquid. GC 45 % Areas analysis indicated the presence of phenol (5.3.g., 43% Methyl (Methylthio)phenols) recovered), ortho-(methylthio)phenol (5.1 g, 41% Time, Hr. T, C. Disulfide Phenol Ortho Para Di yield), para-(methylthio)phenol (2.3 g), and di(methyl O 120 6.6 93.4 O O O thio)phenols (2.2 g). 1.5 146 3. 53.8 16.8 25.5 0.8 The reaction above was repeated using identical 50 6.5 84 0.5 48.8 23.8 12.6 12. amounts of phenol and methyl disulfide and 2.9 g of the 8.0 180 O 47.9 20.6 13.1 13.6 solid H ELZ-20 catalyst recovered from the reaction above. This mixture was heated and followed by GC as The mixture was cooled to room temperature and above. filtered. The catalyst was washed several times with The reaction was stopped after 4 hours at which time 55 ether and allowed to dry. The filtrate and ether wash the temperature was 174° C. Work-up as before yielded ings were combined, and volatiles were removed on a recovered catalyst weighing 2.9 g and 15.4 g of liquid rotary flash evaporator. GC analysis indicated the pres products. GC analysts indicated the presence of phenol ence of phenol (5.3.g. 42% recovered), ortho(methylthi (5.3 g, 43% recovered), ortho-(methylthio)phenol (5.0 o)phenol (5.2 g 41% yield), para-(methylthio)phenol g, 40% yield), para-methylthio)phenol (1.9 g) and di (2.0 g, and di-(methylthio)phenols (2.0 g). (methylthio)phenols (2.2 g). The reaction was again repeated using identical EXAMPLES 29 AND 30 amounts of phenol and methyl disulfide and 2.8g of the Preparation of 2-(Methylthio-4-substituted phenols solid HELZ-20 catalyst recovered from the first repeti Amorphous silica-alumina (2.5g, 25% Al2O3, Grade tion. The mixture was heated for 4 hours at which time 65 980-25, Davison Chemical Division, W. R. Grace Co.), the temperature was 179 C. After work-up as before, 4-substituted phenol (Table below), and methyl disul GC analysis indicated the presence of phenol (5.7 g, fide (8.4g, 0.089 moles) were combined and heated at 46% recovered), ortho-(methylthio)phenol (5.1 g, 41% reflux under nitrogen for 11-11.5 hours during which 4,792,633 15 16 temperature increased to 180 C. Methyl mercaptan was allowed to escape continuously. The mixture was EXAMPLE 35 cooled to room temperature and filtered. The catalyst Preparation of 2-Methylthio-4-methylphenol was washed several times with ether. The filtrate and p-Cresol (1.2g, 0.01 mole), para-(methylthio)phenol ether washings were combined, and volatiles were re- 5 (3.0 g, 0.02 mole), and HELZ-20 from Example 27 (1.0 moved on a rotary flashed evaporator. GC analysis g) were combined and heated at 176' C. for 14 hours. indicated the presence of only two major components, The mixture was cooled to room temperature and fil i.e., the 4-substituted phenol starting material and 2 tered. The catalyst was washed several times with methylthio-4-substituted phenol in the yields indicated ether. The filtrate and ether washings were combined, in Table VI. 10 and volatiles were removed on a rotary flash evapora TABLE VI tor. GC analysis indicated the presence of 2-methylthio 4-Substituted 4-methylphenol (0.9 g, 56% yield). Phenol Products EXAMPLE 36 Starting 2-Methyl 15 Reactant Phenol Material thio Preparation of ortho-(Methylthio)phenol 4-Substi- grams, 76 grams, Phenol (25.0 g, 0.27 moles), methyl disulfide (16.8g, Example tet grams recovered % yield 0.18 moles), and H ELZ-20 from Example 27 (5.0 g) 29 C1 17. 8.8, 52 7.4, 44 were combined and heated under nitrogen at reflux for 30 CH3 4.4 6.3, 44 10.6, 77 4.5 hours during which the temperature increased to 189 C. and GC analysis indicated no further increase in the amount of ortho-(methylthio)phenol. Methyl mer EXAMPLE 31 captan was allowed to escape continuously. The mix Preparation of ortho-(Methylthio)phenol ture was cooled to room temperature and filtered. The Para-(methylthio)phenol (4.0 g, 0.029 moles) and H 25 catalyst was washed with ether several times. The fil trate and ether washings were combined and vacuum ELZ-20 from Example 27 (1.0 g) were combined and distilled through a 5'Vigreux column collecting a frac heated under nitrogen for 15 hours at 168-177 C. The tion weighting 18.5 g that distilled at 98-167 C. at 30 mixture was filtered and the catalyst was washed with mm mercury. GC analysis of this fraction indicated ether several times. The filtrate and ether washings 30 only two major components, phenol (8.5g, 34% recov were combined, and volatiles were removed on a rotary ered) and ortho-(methylthio)phenol (8.8 g., 35% yield). flash evaporator. GC analysis indicated the presence of GC analysis indicated that the undistilled portion (9.6 g) phenol, ortho-(methylthio)phenol, para-(methylthio)- was almost entirely para-(methylthio)phenol and di phenol, and di-(methylthio)phenols in a 1.5:2.0:1.0:1.5 (methylthio)phenols. The undistilled portion (9.6 g) was molar ratio, respectively. The yield of ortho-(methylthi 35 combined with phenol (6.6 g., 0.07 moles) and catalyst o)phenol was 21%. from the previous reaction (6.8 g), and heated at 175 C. EXAMPLES 32-34 for 6 hours. Additional H ELZ-20 (2.0 g) was added and the mixture was heated for an additional 18 hours at Preparation of ortho-(Methylthio)phenol 175 C. The mixture was cooled to room temperature Phenol (4.0 g, 0.043 moles), para-(methylthio)phenol and filtered. The catalyst was washed with ether several (6.0 g, 0.043 moles), and catalyst (2.0 g, Examples 32 times. The filtrate and ether washings were combined, and 33 in Table below) were combined and heated and volatiles were removed on a rotary flash evapora under nitrogen for the times and at the temperatures tor. GC analysis indicated the presence of phenol (4.6 indicated. The mixtures were cooled to room tempera g), ortho-(methylthio)phenol (3.8 g), para(methylthio)- ture and filtered. The solid catalyst was washed several 45 phenol (2.0 g), and di-(methythio)phenol (2.8 g). times with ether. The filtrate and ether washings were combined, and volatiles were removed on a rotary flash EXAMPLE 27 evaporator. GC analysis indicated the presence of phe Preparation of ortho-(Methylthio)phenol nol, ortho-(methylthio)phenol, para-(methylthio)- 50 The undistilled portion from Example 19 (including phenol, and di-(methylthio)phenols. Yields of ortho catalyst) was combined with phenol (17.5 g, 0.19 (methylthio)phenol are given in the Table below. moles), methyl disulfide (7.5 g, 0.08 moles), and amor In Example 34, phenol (4.0 g), para-(methylthio)- phous silica-alumina (5.0g, 25% Al2O3, Grade 980-25, phenol (6.0 g), and p-toluenesulfonic acid hydrate (0.8 Davison Chemical Division, W. R. Grace Co.). The g) were combined and reacted as above for the time and 55 mixture was heated a total of 14 hours during which the temperature given in the Table below. The mixture was temperature increased to 180° C. The mixture was worked-up and analyzed as in Example 26 above. Yield cooled to room temperature, filtered, and the catalyst of ortho-(methylthio)phenol is given in Table VII be washed with ether several times. The filtrate and ether low. washings were combined, and volatiles were removed TABLE VII on a rotary flash evaporator. GC analysis indicated the o-(Methyl presence of phenol (9.0 g, 51% recovered based on Time, thio)phenol, phenol added above), ortho-(methylthio)phenol (8.4g, Example Catalyst Hr. T, C. % Yield 75% based on methyl disulfide used above), para-(me 33 HELZ-20 8 75 46 thylthio)phenol (2.1 g), and di-(methylthio)phenols (4.6 33 Amberlyst (R) 15 7 72 47 65 g). 34 p-Toluenesulfonic 6.5 173 44 I claim: Acid 1. A process for the preparation of ortho(alkylthio- or arylthio)phenols wherein the alkylthio- and arylthio 4,792,633 17 18 moieties are of the formula RS-which comprises react ortho-(alkylthio- or arylthio)phenols and mixtures of ing a corresponding phenol having the formula the foregoing. 3. The process of claim 1 wherein the alumino-silicate OH I is amorphous and has an alumina content of 5-90% by weight based upon the weight of the silicate. 4. The process of claim 1 wherein the alumino-silicate is amorphous and has an alumina content of 10-60% by weight based upon the weight of the silicate. 5. The process of claim 1 wherein the alumino-silicate 10 is amorphousand has an alumina content of 25-30% by wherein weight based upon the weight of the silicate. X and Y are independently selected from the group 6. The process of claim 2 wherein the alumino-silicate consisting of H, OH, C1-C5 alkyl, OR1, Cl, F, I, Br, is amorphous and has an alumina content of 5-90% by aryl or aryl substituted with C1-C6 alkyl, OR1, Cl, 15 weight based upon the weight of the silicate. F, I or Br, or when X and Y are on adjacent carbon 7. The process of claim 2 wherein the alumino-silicate atoms, they may be taken together to form is amorphous and has an alumina content of 10-60% by CH=CH-CH=CH; and weight based upon the weight of the silicate. R1 is C1-C6 alkyl or phenyl; 8. The process of claim 2 wherein the alumino-silicate provided that X and Y cannot simultaneously be 20 is amorphous and has an alumina content of 25-30% by OH, and when X or Y is OH and the other is weight based upon the weight of the silicate. hydrogen, the OH cannot be in the para position; 9. The process of claim 1 wherein the alumino-silicate with a compound selected from the group consisting of is a zeolite. alkyl or aryl disulfides having the formula (RS)2 10. The process of claim 9 wherein the zeolite is a H wherein R is C1-C6 alkyl or aryl wherein aryl is uns 25 zeolite having a pore size greater than about 5 A. bustituted or substituted with one or more substitu 11. The process of claim 2 wherein the zeolite is a H ents selected from the group consisting of C1-C6 zeolite having a pore size greater than about 5 A. alkyl, Cl, F, I, Br, OR1, aryl where R1 is C1-C6 12. The process of claim 11 wherein the zeolite has a alkyl or phenyl Si/Al ratio in the range of about 2.4 to 1000. provided that when R is C4-C6 alkyl, the carbon 30 13. The process of claim 12 wherein the zeolite is bonded to the heteroatom must be substituted by prepared by calcining an NH4 zeolite under deep bed one or two hydrogen atoms; or (alkylthio- or aryl conditions. thio)phenols, or mixtures of the foregoing wherein 14. The process of claim 1 wherein the alumino-sili the alkylthio- and arylthio- moieties are of the for cate is an HY zeolite. mula RS- and the phenol moieties correspond to 35 15. The process of claim 1 wherein the alumino-sili Formula I above in the presence of an aluminosili cate is an H. Beta zeolite. cate having catalytically active acidic sites. 16. The process of claim 1 wherein the alumino-sili 2. The process of claim 1 wherein the resulting or cate is an H ZSM-5 zeolite. tho(alkylthio- or arylthio)phenols are selected from the 17. The process of claim 1 wherein the alumino-sili group consisting of ortho,ortho-di(alkylthio- or arylthi cate is an H mordenite zeolite. o)phenols; orthipara-di(alkylthio-or arylthio)phenols; k k e ck 3k